Ketone adducts



United States Patent 3,393,223 KETONE ADDUCTS Pasquale Lombardo, Chevy Chase, Md., assignor to A]- lied Chemical Corporation, New York, N.Y., a corporation of New York No Drawing. Continuation-impart of application Ser. No. 266,215, Mar. 19, 1963. This application Dec. 23, 1966, Ser. No. 606,595

9 Claims. (Cl. 260-468) I 0 c1 c1 This polycyclic ketone may be prepared in known manner by hydrolyzing the reaction product of hexachlorocyclopentadiene and sulfur trioxide.

An object of the present invention is to provide new ketone adducts exhibiting high pesticidal activity.

Another object of the invention is to provide new pesticidal compositions containing the ketone adducts as active ingredients.

Still another object of the invention is to provide a method for combatting pests, especially insects, comprising contacting the pests with pesticidal compositions containing the ketone adducts as active ingredients.

It is a further object of the invention to provide a simple and economical method for preparing the ketone r The ketone adducts contemplated by this invention comprise those obtained -by reacting the polycyclic ketone with a ketone having a general formula selected from the group consisting of RCH COR in which R is a member of the group consisting of hydrogen and methyl and R is a member of the group consisting of alkyl, aryl and acyl radicals,

in which R is a member of the group consisting of hydrogen and alkyl radicals, and

in which R is a member of the group consisting of hydrogen and alkyl radicals.

The ketone adducts of my invention, therefore, have the following general formula wherein A represents a radical resulting from the removal of hydrogen from one of the carbons adjacent the CO group in the compounds listed above.

The new adducts thus include the three groups of compounds and their preparation as shown in the equations below wherein the R substituents are as defined above.

H 0 40 u 1 0 c1 C1 C1 C2 u cl L C1 C1 01 C1 C1 cl 8 C1 C1 B2 C1 C1 01' C1 C1. C1

01 C. ll 01 1 c1 c1 0 c1 c1 cl\ :1

01 C1 C1 C1 3 In the compounds wherein A is derived from water. The water can also be removed during reaction,

1 as described below. RCHzCOR Although the reactants may be employed in mol ratio the alkyl and aryl radicals represented by R may be substituted or unsubstituted. The substituted alkyl radicals include, but are not limited to, arylalkyl, haloalkyl and carboalkoxyalkyl. The unsubstituted alkyl radicals preferably contain 1 to 9 carbon atoms, while the alkyl portion of the substituted alkyl radicals preferably contains 1 to 4 carbon atoms. The alkoxy portion of the carboalkoxyalkyl radicals also preferably contains 1 to 4 carbon atoms. Among the compounds in this category are 2-octanone, 2-nonanone, Z-heptanone, 2-undecanone, acetone, 4-methyl-2-pentanone, 3-pentanone, Z-butanone, 2-pentanone, diacetyl, chloroacetone, phenylacetone, acetophenoue, 3-methyl-2-butanone, ethyl levulinate, ethyl pyruvate, butyl levulinate, methyl pyruvate, etc.

In the compounds wherein A is derived from the alkyl radical preferably contains '1 to 3 carbon atoms. Compounds in this category include cyclopentanone, 2 methylcyclopentanone, 3-Inethylcyclopentanone, 4-rnethylcyclopentanone, etc.

In the compounds wherein A is derived from the alkyl radical preferably contains 1 to 3 carbon atoms. Compounds in this category include cyclohexanoue, 2- methylcyclohexanone, 3-methylcyclohexanone, etc.

The ketone adducts of the invention may be prepared in simple and economical manner by reacting the polycyclic ketone with the desired ketone, in mol ratio of about 0.5 to 2 mols of polycyclic ketone per mol of ketone, at temperature ranging from room temperature to about 250 C.

If the ketone is available in hydrate form, it can be dehydrated before reaction by-heating it in an oven at temperature of about 135 to 150 C. or by refluxing it with an aromatic solvent such as xylene to remove the of about 0.5 to 2 mols of polycyclic ketone per mol of ketone, it is preferred to use approximately equimolar proportions of the reactants.

The reaction is carried out at room temperature to about 250 C., usually at temperature of about 55 to 200 C. The reaction temperature is preferably the reflux temperature of the reaction mixture.

If desired, the reaction may be carried out in the presence of an organic solvent. The solvent must be inert to the reactants and the desired ketone adduct. Among the suitable solvents are aliphatic or aromatic hydrocarbons such as Xylene, toluene, benzene, petroleum ether, methylene chloride, etc. The solvent serves to keep the adduct in solution. Moreover, if the polycyclic ketone is employed in hydrate form, the solvent enables dehydration thereof during the reaction.

The ketone adducts may be recovered from the reaction mixture by procedures known in the art, as by precipitation with a non-solvent, e. g., hexane, followed by filtration and drying. The adducts may be purified, for example, by recrystallization from hexane.

The following examples are typical of preparation of the ketone adducts of this invention. In the examples, parts are by weight. Further, in the structures given for the adducts designated as l l C1 EXAMPLE 1 to a pot temperature of 85 C. Since acetone boils at 56 0, most of the unreacted acetone was removed. The remaining unreacted acetone was removed by stripping in vacuo. This procedure was repeated twice, resulting in production of 53 parts of solid polycyclic ketoneacetone adduct (96% yield),

The adduct melted at 342348 C. with decomposition, and its infrared spectrum showed hydroxyl absorption at 2.78 microns and carbonyl absorption at 5.85 microns. It has the following structure ll CH 0 CH EXAMPLE 2 CH2C-- CH2 CH- CH3 EXAMPLE 3 56 parts of polycyclic ketone hydrate (4 mols H O) were mixed with 215 parts of xylene, and the mixture was refluxed. The water formed was azeotroped out of the mixture over a period of 3 hours. 14.4 parts of ethyl levulinate were then added to the solution, and the mixture was refluxed for 18 hours. The solution was filtered and the filtrate stripped of solvent in vacuo to yield a viscous oil. Trituration of the oil with hexane gave 38 parts (60% yield) of solid polycyclic ketone-ethyl levulinate adduct.

The adduct had a melting point of 748l C., and its infrared spectrum showed hydroxyl absorption at 2.98 microns and carbonyl absorption at 5.80 and 5.88 microns. It has the following structure 6 EXAMPLE 4 56 parts of polycyclic ketone (4 mols H O) were refluxed with 225 parts of xylene to azeotropically remove water. 17 parts of cyclopentanone were added to the xylene solution, and the mixture was refluxed overnight. The solution was then filtered to remove insoluble material and stripped to yield an oil. The oil was triturated with hexane to give 37 parts (64% yield) of solid polycyclic ketone-cyclopentanone adduct.

The adduct was recrystallized from hexanemethylene chloride mixture to produce a purified product having a melting point of -197 C. The infrared spectrum of the adduct showed hydroxyl absorption at 2.96 microns, carbon-hydrogen absorption at 3.34, 3.44, 6.88 and 7.12 microns and carbonyl absorption at 5.77 microns. It has the following structure EXAMPLE 5 I *clt c -tcr1 014 EXAMPLE 6 Polycyclic ketone-Z-nonanone adduct was prepared by the procedure described in Example 5. 44 parts of solid adduct, constituting a yield of 70%, were obtained.

The adduct had a melting point of 7076 C., and its infrared spectrum showed hydroxyl absorption at 2.96 microns and carbonyl absorption at 5.88 microns. It has the following structure 9 CH2- 0 -(cu CH3 EXAMPLE 7 Polycyclic ketone-Z-heptanone adduct was prepared by the method described in Example 5. 27 parts of solid adduct were initially obtained, and an additional 11 parts ll ca c; (CH -CH EXAMPLE 8 Polycyclic ketone-Z-undecanone adduct was prepared by the procedure described in Example 5. A total of 38 parts of solid adduct were obtained in two crops, representing a 50% yield.

The adduct had a melting point of 6871 C., and its infrared spectrum showed hydroxyl absorption at 3.00 microns and carbonyl absorption at 5.90 microns. It has the following structure ll CH -C (K l -CH EXAMPLE 9 0 OH H V H pa c Ca -c 3 CH3 EXAMPLE 10 56 parts of polycyclic ketone hydrate (4 mols H O) were mixed with 81 parts of Z-butanone. The mixture was boiled down on a steam bath four times to obtain a product comprising solid polycyclic ketone-Z-butanone adduct.

The adduct had a melting point of 346350 C. with decomposition, and its infrared spectrum showed hydrox- 8 yl absorption at 2.90 microns and carbonyl absorption at 5.86 and 5.99 microns. It has the following structure EXAMPLE 11 56 parts of polycyclic ketone hydrate (4 mols H O) were mixed with 49 parts of Z-pentanone, and the mixture was heated at reflux for 4 hours. Excess Z-pentan'one was stripped off. Additional 2-pentanone was added, and the mixture was heated to C. and then stripped in vacuo. 51 parts of solid polycyclic ketone-Z-pentanone adduct were obtained.

The adduct had a melting point of 84160 C. and its infrared spectrum showed hydroxyl absorption at 2.90 microns and carbonyl absorption at 5.85 and 5.98 microns. It has the following structure on o EXAMPLE 12 56 parts of polycyclic ketone hydrate (4 mols H O) were mixed with 20 parts of cyclohexanone. 172 parts of xylene were added to the mixture, and the water formed was azeotroped out. The mixture was heated at 120 C. for several hours and then stripped in vacuo. An additional 20 parts of cyclohexanone and 43 parts of xylene were added, and the mixture was heated for 10 hours at C. The mixture was then stripped in vacuo to a small volume. Partial crystallization occurred, and 20 parts of solid polycyclic ketone-cyclohexanone adduct were obtained.

The adduct had a melting point of 166171 C., and its infrared spectrum showed hydroxyl absorption at 3.02 microns and carbonyl absorption at 5.88 microns. It has the following structure EXAMPLE 13 56 parts of polycyclic ketone hydrate (4 mols H O) were azeotroped free of water in xylene. 8.6 parts of diacetyl were then added, and the mixture was refluxed overnight. Solvent was stripped from the mixture in vacuo to yield a viscous solid. The solid was boiled up with hexane, filtered and washed with hexane. 42 parts of solid polycyclic ketone diacetyl adduct were obtained.

The adduct had a melting point of 122350 C. with decomposition, and its infrared spectrum showed hydroxyl absorption at 2.80 microns and carbonyl absorption at 5.65 and 5.75 microns. It has the following structure on 9 9 CH2C-C-CH3 EXAMPLE 14 56 parts of polycyclic ketone hydrate (4 mols H O) were azeotroped free of water in 215 parts of xylene. 9.3 parts of chloroacetone were then added, and the mixture was refluxed overnight. Solevent was stripped from the mixture in vacuo, and the resultant solid was tr-iturated with hexane and filtered off. An additional 10 parts of chloroacetone were added to the solid along with 172 parts of xylene. The hexane and water were distilled ofl, and the mixture was refluxed overnight. Solvent was stripped in vacuo, and the resultant solid was boiled up with hexane, filtered off and washed with hexane. 37 parts (64% yield) of solid polycyclic ketone-chloroacetone adducts were obtained.

The adduct had a melting point of 145l52 C., and its infrared spectrumshowed hydroxyl absorption at 2.80 microns and carbonyl absorption at 5.76 microns. It has the following structure EXAMPLE 15 56 parts of polycyclic ketone hydrate (4 mols H O) were azeotroped free of water in 215 of xylene. 13.5 parts of phenylacetone were added to the mixture, and it was refluxed for 60 hours. Solvent was stripped from the mixture in vacuo to yield an oil which solidified overnight. The solid was triturated with hexane, filtered OE and washed with hexane. 42 parts (67% yield) of solid polycyclic ketone-phenylacetone adduct were obtained.

The adduct exhibited a melting point of 140143 C., and its infrared spectrum showed hydroxyl absorption at 2.93 microns and carbonyl absorption at 5.87 microns. It has the following structure 10 EXAMPLE 16 56 parts of polycyclic ketone hydrate (4 mols H O) were azeotroped free of water in 215 parts of xylene. 12 parts of acetophenone were added, and the mixture was refluxed overnight. The mixture was filtered and then stripped of solvent in vacuo to yield a solid. The solid was triturated with hexane, filtered ofl and washed with hexane. 51.5 parts (84% yield) of solid polycyclic ketoneacetophenone adduct were obtained.

The adduct was recrystallized from hexane-methylene chloride mixture to produce a purified product having a melting point of 152-l53 C. The infrared spectrum of the adduct showed hydroxyl absorption at 2.95 microns, carbonhydrogen absorption at 3.23 and 3.41 microns, carbonyl absorption at 5.98 microns and aromatic ring vibrations at 6.25, 6.31 and 6.89 microns. It has the following structure 56 parts of polycyclic ketone hydrate (4 mols H O) were azeotroped free of water in 259 parts of xylene. 8.6 parts of 3-methyl-2-butanone were added, and the mixture was refluxed overnight. The solution was filtered and then stripped of solvent in vacuo. An oil resulted which solidified upon trituration with hexane. The solid was filtered off and washed with hexane. 36 parts (62% yield) of solid polycyclic ketone-3-methyl-2-butanone adduct were obtained.

The adduct exhibited a melting point of l39143 C., and its infrared spectrum showed hydroxyl absorption at 3.01 microns and carbonyl absorption at 5.92 microns. It has the following structure ii CH C (ill-CH3 EXAMPLE 13 1 1 EXAMPLE 19 56 parts of polycyclic ketone hydrate (4 mols H O) were azeotroped free of water in 215 parts of refluxing xylene. 16 parts of tert.-butylacetoacetate were added, and the mixture was heated at 100-1l0 C. overnight. The mixture was then stripped of solvent in vacuo to produce 62 parts of a viscous, dark oil comprising polycyclic ketone-tert.-butylacetoacetate adduct.

The infrared spectrum of the adduct showed hydroxyl absorption at 2.93 microns and carbonyl absorption at 5.74 and 5.87 microns. It has the following structure OH O O EXAMPLE 20 49 parts of anhydrous polycyclic ketone and 12 parts of ethyl pyruvate were allowed to react in refluxing toluene over a period of 4 /2 days. Solvent was stripped from the mixture in vacuo to obtain a slightly oily solid. The solid was triturated with hexane, filtered off and washed with hexane to obtain 38 parts of air-dried solid comprising polycyclic ketone-ethyl pyruvate adduct. The adduct was recrystallized from 60 parts of chloroform to obtain 12 parts of purified adduct having a melting point of 240-247 C. Additional adduct was obtained by boiling down the filtrate and allowing it to crystallize.

The infrared spectrum of the adduct showed hydroxyl absorption at 2.92 microns and carbonyl absorption at 49 parts of anhydrous polycyclic ketone were prepared by azeotropically distilling water out of ketone hydrate (4 mols H O) using toluene. 17.2 parts of butyl levulinate were added, and the mixture was refluxed overnight. Solvent was stripped in vacuo to yield an oily solid. The solid was triturated with hexane, filtered oif and washed with hexane. The solid and filtrate were then combined. 176 parts of xylene were added, and solvent was re moved to a pot temperature of 140 C. The resulting mass was then allowed to reflux for a few days. Solvent was then stripped from the mass in vacuo to obtain a dark oil. The oil was dissolved in a small amount of hot hexane and cooled. 45 parts (68% yield) of solid polycyclic ketone-butyl levulinate crystallized out.

The adduct exhibited a melting point of 9496 C. after recrystallization from hexane-methylene chloride mixture. The infrared spectrum of the adduct showed hydroxyl absorption at 2.91 microns and carbonyl absorption at 5.77 and 5.87 microns. It has the following structure I cn b ca ca -co -(ca ca EXAMPLE 22 53 parts of polycyclic ketone hydrate (4 mols H 0) 0 were azeotroped free of water in 172 parts of refluxing xylene. 10 parts of methyl pyruvate were added, and the mixture was refluxed for 41 hours. Insoluble material was filtered off, and the filtrate was stripped of solvent in vacuo. A semi-solid was obtained which was triturated with hexane, cooled, filtered off and washed with hexane. 42 parts of solid polycyclic ketone-methyl pyruvate were obtained.

The adduct was recrystallized from chloroform-methylene chloride mixture to obtain a purified product having a melting point of 248-251 C. The infrared spectrum of the adduct showed hydroxyl absorption at 2.92 microns and carbonyl absorption at 5.62 and 5.92 microns. It has the following structure The ketone adducts of this invention may be applied to pests, especially insects, as is but are advantageously incorporated as ingredients in suitable liquid or solid carriers to provide pesticidal spray or dust compositions.

The liquid pesticidal compositions generally contain in proportions 'by weight about 10 to 25% of the adduct as active ingredient, about 65 to 88 of an aromatic solvent and about 2 to 10% of a suitable wetting or emulsifying agent, such as diglycol oleate, pisooctyl phenyl ether of polyethylene glycol, blends of alkyl aryl polyether alcohols with alkyl aryl sulfonates and blends of polyoxyethylene sorbitan esters of mixed fatty and resin acids with alkyl aryl sulfonates. The resulting concentrate solution is diluted or admixed with water to form an aqueous dispersion or emulsion suitable for spray application containing about 0.001 to 0.1% by weight of active ingredient.

Representative aromatic solvents which may be used in preparing the liquid pesticidal compositions include xylene, high aromatic solvents, methylated naphthalenes, heavy aromatic naphtha, etc. It is an advantage of this invention that the adducts have substantially greater solubility in aromatic solvents than the polycyclic ketone per se.

The wettable powder compositions generally contain in proportions by weight about 25 to 75% of the active ingredient, about 20 to 73% of a finely divided soh'd carrier and about 2 to 5% of suitable wetting and dispersing agent. Typical wetting agents include polyether sulfonates, alkyl aryl sulfonates, etc. Typical dispersing agents include ligninsulfonates, naphthalene sulfonic acid-formaldehyde condensates, etc.

The wettable powder compositions can readily be prepared by mixing or milling the active ingredient with 13 the carrier and wetting agent to a typical particle size of from about 3 to microns. The composition is admixed with water to form an aqueous dispersion suitable for spraying containing about 0.001 to 0.1% by weight of active ingredient.

Representative solid carriers which may be used in preparing the wettable powders include magnesium and aluminum silicates (talc, kaolin clays, attapulgite clays, etc.), carbonates (dolomite, chalk, etc.), materials containing silicic acid (diactomaceous earth), fullers earth, gypsum, sulfur, etc.

The dosage of the active ingredient depends on the particular organisms to be controlled, field conditions, etc., as known in the art. In any event, sufiicient quantity of the active ingredient is used to provide the desired toxicity.

Examplary tests of the ketone adducts of the present invention are set forth below:

A C1 Cl C1 C1 C1 Percent Kill Mexican Southern Active Ingredient Formulation Bean Army Beetle Worms Larvae Polycyclic ketone-cyclopentanone 2 pounds active ingredient per 100 100 adduct. 100 gallons water. Polycyclic ketone-2-octancne do 100 addnct. Polycyclic ketone-2-nonanone do 80 a net. Polycyclic ketone-2-heptanone do 10D adduct. Polycyclic ketone-acetone adduct do t 100 100 Polycyclic ket0ne-4-methyl-2- t. do 100 100 pentanone adduct. Polycyclic ketone 3-pentanone d0 100 100 adduct. Polycyclic ketone-2-butanone do 100 100 adduct. Polycyclic ketone2-pentanone do 100 100 ad u Polygyclzic ketone-cyclohexanone do 100 100 a uc Polycyclic ketone-diacetyl ad- 8 pounds wettable powder com- 100 not. position per 100 gallons water. Polycyclic ketone-chloroacetone do. 100

adduct. Polycyclic ketone-phenylacetone l -d0.* 80

addu Polycyclic ketonc-acetophenone do. 100

adduct. Polycyclic ketone-3-methyl-2- do. 100

butanone addnct. Polycyclic ketone-ethyl levuli- 2 pounds active ingredient per 100 100 nate adduct. 100 gallons water. Polycyclic ketone-ethylacetodo 100 100 acetate adduct. Polycyclic ketone-tert.-butyl- 8 pounds wettable powder com- 100 100 acetoacetate adduct. position per 100 gallons water. Polycyclic ketone-ethyl pyruvate 2 pounds active ingredient per 100 adduct. 100 gallons acetone-water solution (1 1). Polycyclic ketone-butyl levulido 100 100 nate adduct. Polycyclic ketone-methyl pyrudo 80 90 vate adduct.

25.0% active ingredient, 73.5% Attaclay (attapulgite clay carrier), 0.75% Elvanol" 51-05 (water-soluble synthetic polyvinyl alcohol dispersing agent), 0.75% Nacconol SW" (alkyl aryl sulfonate Wetting agent).

The tests on toxicity to Mexican bean beetle larvae (Epilachna varz'vestis) were carried out by spraying horticultural (cranberry) bean plants with indicated formulation and allowing the plants to dry. The larvae were confined to the treated foliage by means of Wire cages. Record of kill was made 3 days after treatment.

The tests on Southern armyworms (Prodem'a erz'danz'a) were carried out by spraying horticultural (cranberry) bean plants with the indicated formulation and allowing the plants to dry. The armyworms were confined to the treated foliage by means of wire cages. Mortality count was made three days after treatment.

Since various changes and modifications may be made in this invention without departing from the spirit thereof, the invention is deemed to be limited only by the scope of the appended claims.

wherein A is a member selected from the group consisting of atoms, carboalkoxy radicals in which the alkoxy contains 1 to 2 carbon atoms, phenyl and acetyl;

wherein R is a member of the group consisting of hydrogen and alkyl radicals containing 1 to 3 carbon atoms;

wherein R is a member of the group consisting of hydrogen and alkyl radicals containing 1 to 3 carbon atoms.

2. A compound of the formula wherein R is a member selected from the group consisting of hydrogen and methyl; R represents a member selected from the group consisting of unsubstituted alkyl radicals containing 1 to 9 carbon atoms, arylalkyl radicals in which the alkyl group contains 1 to 4 carbon atoms, haloalkyl radicals in which the alkyl contains 1 to 4 carbon atoms, carboalkoxyalkyl radicals in which the alkyl contains 1 to 4 carbon atoms and the alkoxy contains 1 to 4 carbon atoms, carboalkoxy radicals in which the alkoxy contains 1 to 2 carbon atoms, phenyl and acetyl.

3. The compound according to claim 2 wherein R is hydrogen and R is 4. The compound according to claim 2 wherein R is hydrogen and R is 5. The compound according to claim 1 wherein A is a radical of the formula wherein R is an alkyl group containing 1 to 3 carbon atoms.

16 6. The compound according to claim 1 wherein A is a radical of the formula wherein R is an alkyl group containing 1 to 3 carbon atoms.

7. A process which comprises reacting decachlorooctahydro-l,3,4-metheno-2H-cyclobuta (cd) pentalen-Z-one with a compound having a general formula selected from the group consisting of 1 RCH COR in which R is a member of the group consisting of hydrogen and methyl and R is a member of the group consisting of unsubstituted alkyl radicals containing 1 to 9 carbon atoms, aryl-alkyl radicals in which the alkyl contains 1 to 4 carbon atoms, haloalkyl radicals in which the alkyl contains 1 to 4 carbon atoms, carboalkoxyalkyl radicals in which the alkyl contains 1 to 4 carbon atoms and the alkoxy contains 1 to 4 carbon atoms, carboalkoxy radicals in which the alkoxy contains 1 to 2 carbon atoms, phenyl and acetyl in which R is a member of the group consisting of hydrogen and alkyl radicals containing 1 to 3 carbon atoms and in which R is a member of the group consisting of 'hydrogen and alkyl radicals containing 1 to 3 carbon atoms, in mol ratio of about 0.5 to 2 mols of decachlorooct-ahydro- 1,3,4-metheno-2H-cyclobuta (cd) pentalen-Z-one per mol of compound, at temperature ranging from room temperature to about 250 C.

8. The process of claim 7 in which the reaction is carried out in the presence of an inert organic solvent.

9. A process which comprises reacting approximately equimolar proportions of decachlorooctahydro-1,3,4- metheno-ZH-cyclobuta (cd) pentalen-Z-one and a compound having a general formula selected from the group consisting of RCH COR .1 7 1 8 in which R is a member of the group consisting of hydroin which R of a member of the group consisting of hydrogen and alkyl radicals containing 1 to 3 carbon atoms and gen and alkyl radicals, containing 1 to 3 carbon atoms (3) O at temperature of about 55 to 200 C. in the presence ll of an inert organic solvent.

No references cited.

LORRAINE A. WEINBERGER, Primary Examiner.

P. I. KILLOS, Assistant Examiner. 

1. AS NEW COMPOSITONS OF MATTER THE KETONIC COMPOUNDS OF THE FORMULA 